The reaction of K-2[PtCl4] with three 6-alkyl-2,2'-bipyridines HL, (N2C10H7Ri R = CH2Me, HLet; CHMe2, HLip; CH2CMe3, HLnp) affords five- and six-membered cyclometallated complexes [Pt(L)Cl] where L is a terdentate N,N,C anionic ligand which originates from HL through direct activation of a C(sp(3))-H bond. In the case of HLip, metallation generates a stereogenic carbon atom beta to the metal. Complex 5, [Pt(L-np)Cl], having an uncommon six-membered ring containing a Pt-C(sp(3)) bond, was studied in depth in solution, by means of 1- and 2- dimensional NMR spectroscopy, and in the solid state by X-ray diffraction. Differences are observed in the behaviour of these ligands: thus with HLet an adduct, [Pt(HLet)Cl-2], was also isolated and its structure was determined by X-ray diffraction. In the metallated species, the fourth ligand, Cl, can easily be substituted by neutral or anionic ligands (CO, PPh3, CN-). The metallated species react with potentially bidentate ligands L'-L" [Ph2PCH2PPh2 (dppm), Ph2P(CH2)(2)PPh2 (dppe), Ph2P(CH2)(2)AsPh2 (dppae)] to give, with different Pt:L ratios, mononuclear [Pt(L)(L'-L")](+) or dinuclear [(L)Pt(mu-L'-L")Pt(L)](++) cationic species. In the second case an uncommon unsupported L'-L" bridge is present. The cyclometallated species are stable in air and moisture, and the N,N,C system is rather robust. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

The reaction of K2[PtCl4] with three 6-alkyl-2,2-bipyridines HL, (N2C10H7R; R = CH2Me, HLet; CHMe2, HLip; CH2CMe3, HLnp) affords five- and six-membered cyclometallated complexes [Pt(L)Cl] where L is a terdentate N,N,C anionic ligand which originates from HL through direct activation of a C(sp3)−H bond. In the case of HLip, metallation generates a stereogenic carbon atom β to the metal. Complex 5, [Pt(Lnp)Cl], having an uncommon six-membered ring containing a Pt−C(sp3) bond, was studied in depth in solution, by means of 1- and 2- dimensional NMR spectroscopy, and in the solid state by X-ray diffraction. Differences are observed in the behaviour of these ligands: thus with HLet an adduct, [Pt(HLet)Cl2], was also isolated and its structure was determi-ned by X-ray diffraction. In the metallated species, the fourth ligand, Cl, can easily be substituted by neutral or anionic ligands (CO, PPh3, CN−). The metallated species react with potentially bidentate ligands L−L [Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)2AsPh2 (dppae)] to give, with different Pt:L ratios, mononuclear [Pt(L)(L−L)]+ or dinuclear [(L)Pt(μ−L−L)Pt(L)]++ cationic species. In the second case an uncommon unsupported L−L bridge is present. The cyclometallated species are stable in air and moisture, and the N,N,C system is rather robust

Metallation of unactivated methyl groups. Platinum(II) derivatives with 6-alkyl-2,2’-bipyridines / Zucca, Antonio; Stoccoro, Sergio; Cinellu, Maria Agostina; Minghetti, G; Manassero, M; Sansoni, M.. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 12(2002), pp. 3336-3346.

Metallation of unactivated methyl groups. Platinum(II) derivatives with 6-alkyl-2,2’-bipyridines

ZUCCA, Antonio;STOCCORO, Sergio;CINELLU, Maria Agostina;
2002-01-01

Abstract

The reaction of K2[PtCl4] with three 6-alkyl-2,2-bipyridines HL, (N2C10H7R; R = CH2Me, HLet; CHMe2, HLip; CH2CMe3, HLnp) affords five- and six-membered cyclometallated complexes [Pt(L)Cl] where L is a terdentate N,N,C anionic ligand which originates from HL through direct activation of a C(sp3)−H bond. In the case of HLip, metallation generates a stereogenic carbon atom β to the metal. Complex 5, [Pt(Lnp)Cl], having an uncommon six-membered ring containing a Pt−C(sp3) bond, was studied in depth in solution, by means of 1- and 2- dimensional NMR spectroscopy, and in the solid state by X-ray diffraction. Differences are observed in the behaviour of these ligands: thus with HLet an adduct, [Pt(HLet)Cl2], was also isolated and its structure was determi-ned by X-ray diffraction. In the metallated species, the fourth ligand, Cl, can easily be substituted by neutral or anionic ligands (CO, PPh3, CN−). The metallated species react with potentially bidentate ligands L−L [Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)2AsPh2 (dppae)] to give, with different Pt:L ratios, mononuclear [Pt(L)(L−L)]+ or dinuclear [(L)Pt(μ−L−L)Pt(L)]++ cationic species. In the second case an uncommon unsupported L−L bridge is present. The cyclometallated species are stable in air and moisture, and the N,N,C system is rather robust
2002
The reaction of K-2[PtCl4] with three 6-alkyl-2,2'-bipyridines HL, (N2C10H7Ri R = CH2Me, HLet; CHMe2, HLip; CH2CMe3, HLnp) affords five- and six-membered cyclometallated complexes [Pt(L)Cl] where L is a terdentate N,N,C anionic ligand which originates from HL through direct activation of a C(sp(3))-H bond. In the case of HLip, metallation generates a stereogenic carbon atom beta to the metal. Complex 5, [Pt(L-np)Cl], having an uncommon six-membered ring containing a Pt-C(sp(3)) bond, was studied in depth in solution, by means of 1- and 2- dimensional NMR spectroscopy, and in the solid state by X-ray diffraction. Differences are observed in the behaviour of these ligands: thus with HLet an adduct, [Pt(HLet)Cl-2], was also isolated and its structure was determined by X-ray diffraction. In the metallated species, the fourth ligand, Cl, can easily be substituted by neutral or anionic ligands (CO, PPh3, CN-). The metallated species react with potentially bidentate ligands L'-L" [Ph2PCH2PPh2 (dppm), Ph2P(CH2)(2)PPh2 (dppe), Ph2P(CH2)(2)AsPh2 (dppae)] to give, with different Pt:L ratios, mononuclear [Pt(L)(L'-L")](+) or dinuclear [(L)Pt(mu-L'-L")Pt(L)](++) cationic species. In the second case an uncommon unsupported L'-L" bridge is present. The cyclometallated species are stable in air and moisture, and the N,N,C system is rather robust. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Metallation of unactivated methyl groups. Platinum(II) derivatives with 6-alkyl-2,2’-bipyridines / Zucca, Antonio; Stoccoro, Sergio; Cinellu, Maria Agostina; Minghetti, G; Manassero, M; Sansoni, M.. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 12(2002), pp. 3336-3346.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11388/60347
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